JP6504912B2 - Method of manufacturing toner - Google Patents

Description

  The present invention relates to a method of producing a toner for visualizing an electrostatic latent image in an image forming method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

  For toners used in electrophotography (apparatus), toner production by a wet method has become mainstream, and production methods such as a suspension polymerization method, an emulsion polymerization method, and a dissolution suspension method have been proposed as a wet toner. .

  Among them, the suspension polymerization method is good at a function-separated core-shell structure, and it is possible to achieve both high durability and developability.

  In addition, introduction of a crystalline resin to the core has been proposed for the purpose of improving low-temperature fixability (Patent Document 1). However, crystalline resins generally have the disadvantage of low elasticity and brittleness, and when introduced into a toner, there is a problem that the durability is lowered even by the suspension polymerization method which is excellent in core-shell structure.

  A hybrid resin of a crystalline resin and an amorphous resin has been proposed as a measure for achieving both low temperature fixability and durability (Patent Document 2). As a result, a toner having both low temperature fixability and durability can be obtained.

JP 2007-71993 A JP, 2010-139659, A

  However, the above-mentioned hybrid resin described in Patent Document 2 needs to have a certain molecular weight to some extent in order to have the characteristics of the crystalline portion and the amorphous portion. As a result of investigations by the present inventors, in the suspension polymerization method, when a resin having such a certain molecular weight is added, there is a problem that the granulation property is deteriorated along with the viscosity increase of the polymerizable monomer composition. It was found to occur.

  Further, in recent years, as the toner performance, further low temperature fixing is required. In order to extend the low temperature fixability, it is necessary to introduce a large amount of the above-described crystalline material into the toner, which is a major issue in terms of productivity.

  The present invention provides a method for producing a toner excellent in fixability and durability while maintaining the granulation property.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, it was found that according to the following method, a toner satisfying the performance can be obtained for the problems.

That is, the present invention is a method for producing a toner having toner particles containing a binder resin,
A step of dispersing a polymerizable monomer composition containing styrene and a macromonomer in an aqueous medium to form particles of the polymerizable monomer composition, and the particles of the polymerizable monomer composition Copolymerizing the styrene and the macromonomer to form the binder resin to obtain toner particles;
Have
The macromonomer is a macromonomer derived from alkyl acrylate or alkyl methacrylate,
The melting point (Tm) of the macromonomer in differential scanning calorimetry (DSC) measurement is 50 ° C. or more and 90 ° C. or less,
The polymerizable monomer composition relates to a method for producing a toner comprising 3% by mass to 40% by mass of the macromonomer.

  According to the present invention, it is possible to manufacture a toner excellent in fixing ability and durability while maintaining the granulation property.

  Hereinafter, preferred embodiments of the present invention will be specifically described.

  The method for producing a toner of the present invention (hereinafter, also simply referred to as the production method of the present invention) is a method for producing a toner having toner particles containing a binder resin, and has the following two steps.

  One is a step of dispersing a polymerizable monomer composition containing styrene and a macromonomer in an aqueous medium to form particles of the polymerizable monomer composition. The second is a step of copolymerizing the styrene and the macromonomer contained in the particles of the polymerizable monomer composition to form the binder resin to obtain toner particles.

  The macromonomer is a macromonomer derived from alkyl acrylate or alkyl methacrylate, and the melting point (Tm) of the macromonomer in the differential scanning calorimetry (DSC) measurement is 50 ° C. or more and 90 ° C. or less. Furthermore, the polymerizable monomer composition contains 3% by mass or more and 40% by mass or less of the macromonomer.

  The present inventors consider the expression mechanism of the present invention as follows.

  The present invention contains styrene and a macromonomer in the polymerizable monomer composition constituting the toner. At the stage of granulation, the above-mentioned styrene and the macromonomer are independently present, and as the resin component which causes the viscosity increase of the polymerizable monomer composition, the macromonomer and, if necessary, the polar resin which is a shell resin And charge control resins only. Therefore, it is presumed that even if a relatively large amount of macromonomer is contained, the increase in viscosity of the polymerizable monomer composition is suppressed, and a sharp particle size distribution can be obtained without disturbing the granulation property.

  Then, in the polymerization reaction step, styrene and the macromonomer are copolymerized to form a crystalline-amorphous hybrid resin in which the macromonomer is grafted to styrene. This hybrid resin provides a toner excellent in durability and low temperature fixing.

  Macromonomers are derived from alkyl acrylates or alkyl methacrylates. The macromonomer is an alkyl acrylate macromonomer or an alkyl methacrylate macromonomer having a melting point (Tm) of 50 ° C. or more and 90 ° C. or less. If the temperature is lower than 50 ° C., the shelf life is inferior and sufficient durability can not be obtained. When the temperature is higher than 90 ° C., the solubility in the polymerizable monomer composition is poor, and the granulation property is disturbed, and uneven distribution in toner particles occurs, and the durability and the fixing property are inferior.

  The macromonomer is contained in the polymerizable monomer composition at a ratio of 3% by mass to 40% by mass. If the amount is less than 3% by mass, the content of the macromonomer is too small to obtain low temperature fixability. On the other hand, if the amount is more than 40% by mass, the influence of the increase in viscosity due to the addition of the resin appears, and the granulation property is deteriorated. The preferable addition amount is 5% by mass or more and 35% by mass or less.

  The number of polymerizable functional groups per molecule of the macromonomer is preferably 0.7 or more and 1.5 or less. When the number is 0.7 or more, the presence of the non-modified resin is reduced, the hybridization rate with the styrene resin is improved, and the heat resistance and the durability become good. If the number is 1.5 or less, the proportion of polymerizable functional groups at both ends of the macromonomer is not too high, and the fixing gloss is good. In addition, the low temperature fixability is also good.

  The hybrid resin of macromonomer and styrene preferably maintains crystallinity in the toner. Judgment of maintaining crystallinity is judged by the presence or absence of an endothermic peak derived from a macromonomer in DCS. The endothermic peak derived from the macromonomer in the DSC measurement of the toner may overlap with other components such as wax and may be present as a shoulder in that case. The endothermic peak or shoulder derived from the macromonomer in the DSC measurement of the toner indicates that the macromonomer, which is a crystalline resin, is not completely compatible with the binder resin. As a result, the macromonomer crystallizes, and the durability and heat resistance become good.

  The weight average molecular weight (Mw) of the macromonomer is preferably 3,000 or more and 25,000 or less.

  When the weight average molecular weight (Mw) is 3,000 or more, the mechanical stress resistance does not decrease, and the durability is improved. In addition, the heat resistance is also improved. The viscosity raise of the polymerizable monomer composition by resin is suppressed as it is 25000 or less, and favorable granulation property can be maintained.

  The alkyl acrylate or alkyl methacrylate constituting the macromonomer preferably has 12 to 30 carbon atoms in the alkyl portion. Alkyl acrylate or alkyl methacrylate is also referred to hereinafter as alkyl (meth) acrylate.

  The alkyl (meth) acrylate having 12 to 30 carbon atoms in the alkyl portion means lauryl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (Meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, hen icosyl (meth) acrylate, behenyl (meth) acrylate, tricosyl (meth) acrylate, tetracosyl (meth) acrylate, pentacosyl (meth) ) Acrylate, hexacosyl (meth) acrylate, heptacosyl (meth) acrylate, octacosyl (meth) acrylate, nonacosyl (meth) acrylate, tri) It is a Konchiru (meth) acrylate. The combined use of these monomers makes it easy to adjust the melting point of the macromonomer. The use of an alkyl (meth) acrylate having an alkyl moiety of 12 or more carbon atoms results in good heat resistance and durability. The use of an alkyl (meth) acrylate having a carbon number of 30 or less in the alkyl moiety results in good granulation.

  You may make it react other than the said monomer in the range which does not impair the objective of this invention. For example, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, styrene derivatives such as p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; Methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate such as vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, Vinyl hexyl ketone, vinyl isop Vinyl ketones such as ropyl ketone and the like can be mentioned.

  The following method may be mentioned as a method of providing a polymerizable functional group at the end of the acrylic resin polymerized using the above-mentioned monomer. For example, the above monomer is radically polymerized using a polymerization initiator having a hydroxy group at an end such as VA-086 (Wako Pure Chemical Industries), and an acrylic resin having a terminal hydroxy group derived from the initiator is polymerized with styrene Methods of modification with possible polymerizable functional groups can be mentioned.

  Examples of the modification method include modification by Schotten-Baumann reaction using acid colloid, urethane reaction using isocyanate, or the like. Specific examples of the reagent include acryloyl chloride, methacryloyl chloride, p-styrenesulfonic acid chloride, 2-acryloyloxyethyl isocyanate, 2-meacryloyloxyethyl isocyanate and the like.

  Moreover, the method of obtaining a macromonomer by high temperature continuous polymerization like Unexamined-Japanese-Patent No. 2002-363203 as another method is mentioned.

  A polymerizable monomer other than styrene may be used in combination with the polymerizable monomer composition. As a polymerizable monomer suitably used, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene P-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p- Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethyl hexyl acrylate Acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate and 2-benzoyl oxyethyl acrylate Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate , Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl benzoate such as vinyl formate; vinyl methyl Ethers, vinyl ethyl ethers, vinyl ethers such as vinyl isobutyl ether; vinyl methyl ketones, vinyl hexyl ketones, vinyl ketones such as vinyl isopropyl ketone, etc., diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol di Acrylate, 1,6-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate Polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate Methacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4 -(Methacryloxydiethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxypolyether) Xylphenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl naphthalene, divinyl ether, 4,4'-divinylbiphenyl and the like.

  The polymerization initiator may be added simultaneously with the addition of the other additive to the polymerizable monomer, or may be mixed immediately before suspension in the aqueous medium. Further, immediately after granulation, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added before starting the polymerization reaction.

  In the case of a polymerization method using an aqueous medium as in the suspension polymerization method, it is preferable to add a polar resin to the above mixed solution. By adding a polar resin, it is possible to promote the encapsulation of the wax.

  When the polar resin is present in the colorant dispersion suspended in the aqueous medium, the polar resin is easily transferred to the vicinity of the interface between the aqueous medium and the colorant dispersion because of the difference in affinity to water. Polar resin will be unevenly distributed on the surface. As a result, the toner particles have a core-shell structure.

  In addition, if the polar resin used for the shell is selected to have a high melting temperature, even if the binder resin is designed to be melted at a lower temperature for the purpose of low temperature fixation, the occurrence of blocking during storage of the toner It can be suppressed.

  The polar resin is preferably a polyester resin or a carboxyl-containing styrene resin. By using a polyester resin or a carboxyl-containing styrene resin as the polar resin, when the resin is unevenly distributed on the surface of the toner particles to form a shell, the lubricity of the resin itself can be expected.

  As polyester resin, resin which carried out condensation polymerization of the acid ingredient monomer and alcohol ingredient monomer which are mentioned below can be used. As an acid component monomer, terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphoric acid Examples include acids, cyclohexanedicarboxylic acid, and trimellitic acid.

  As an alcohol component monomer, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) And the alkylene glycols and polyalkylene glycols of cyclohexane, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane and pentaerythritol.

  The carboxyl group-containing styrene resin is preferably a styrene-based acrylic acid copolymer, a styrene-based methacrylic acid copolymer, a styrene-based maleic acid copolymer, and the like, and in particular, a styrene-acrylic-acrylic acid-based copolymer Is preferable because it is easy to control the charge amount. The carboxyl group-containing styrenic resin more preferably contains a monomer having a primary or secondary hydroxyl group. As a specific polymer composition, styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-n-butyl acrylate-2-hydroxyethyl methacrylate-methacrylic acid-methacrylic acid methyl copolymer And styrene-α-methylstyrene-2-hydroxyethyl methacrylate-methacrylic acid-methacrylic acid methyl methacrylate copolymer and the like. A resin containing a monomer having a primary or secondary hydroxyl group has a large polarity, and the long-term storage stability is better.

  The polar resin preferably contains 1.0 to 20.0 parts by mass and more preferably 2.0 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin. Is Rukoto.

  A well-known wax component can be used as a wax used for this invention. Specifically, paraffin wax, microcrystalline wax, petroleum wax represented by petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyolefin wax represented by polyethylene and the like Derivatives thereof include natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. The derivatives also include oxides, block copolymers with vinyl monomers, and graft modified products. Also, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes and the like. These can be used alone or in combination.

  Among these, when using a polyolefin, a hydrocarbon wax by a Fischer-Tropsch method, or a petroleum wax, the developability and the transferability tend to be improved, which is preferable. In addition, an antioxidant may be added to these wax components as long as the charging properties of the toner are not affected. Moreover, it is preferable to use 1.0 to 30.0 parts by mass of these wax components with respect to 100 parts by mass of the binder resin.

  The melting point of the wax is preferably in the range of 30 ° C. or more and 120 ° C. or less, more preferably in the range of 60 ° C. or more and 100 ° C. or less.

  Examples of the colorant used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, the following may be mentioned. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62 and 66.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following may be mentioned. C. I. Pigment red 2, 3, 5, 6, 7, 23, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, and C.I. I. Pigment violet 19.

  Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following may be mentioned. C. I. Pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194.

  Examples of the black colorant include carbon black, and those toned in black using the above-mentioned yellow colorant, magenta colorant, and cyan colorant.

  These colorants can be used alone, in a mixture, or in the form of a solid solution. The colorant used in the present invention is selected in terms of hue angle, saturation, lightness, light fastness, OHP transparency, and dispersibility in toner particles.

  The colorant is preferably used in an amount of 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the case of obtaining toner particles by using the suspension polymerization method, it is necessary to pay attention to the polymerization inhibition property and the aqueous phase migration property possessed by the coloring agent, and therefore, coloring with hydrophobic treatment by a substance without polymerization inhibition It is preferred to use an agent. In particular, since many dyes and carbon blacks have polymerization inhibitory properties, care must be taken when used. As a preferable method of hydrophobizing the dye, there is mentioned a method of polymerizing a polymerizable monomer in the presence of the dye in advance to obtain a colored polymer, and the obtained colored polymer can be used as a polymerizable monomer. Add to the composition.

  The carbon black may be treated with a substance (polyorganosiloxane) that reacts with the surface functional group of the carbon black, in addition to the hydrophobization treatment similar to the above-mentioned dye.

  Moreover, you may use a charge control agent as needed. As the charge control agent, known agents can be used, and in particular, a charge control agent that has a high triboelectric charging speed and can stably maintain a constant triboelectric charge amount is preferable. Furthermore, when the toner particles are produced by suspension polymerization, a charge control agent having low polymerization inhibition and substantially free of a soluble matter in an aqueous medium is particularly preferable.

  The charge control agent may be one that controls the toner to be negatively chargeable or one that controls to be positively chargeable. As the negative charge control of the toner, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, metal compounds of oxycarboxylic acids and dicarboxylic acids, aromatic oxycarboxylic acids, aromatic compounds Mono and poly carboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, And charge control resins.

  Examples of charge control agents that control the toner to be positively chargeable include the following. Guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogs thereof and these Lake pigments; Triphenylmethane dyes and their lake pigments (as lakeing agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide And the like; metal salts of higher fatty acids; and charge control resins.

  These charge control agents may be added alone or in combination of two or more.

  Among these charge control agents, metal-containing salicylic acid type compounds are preferable, and those in which the metal is aluminum or zirconium are particularly preferable.

  The addition amount of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin. It is.

  The charge control resin is preferably a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group. As a polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, it is particularly preferable to contain 2 mass% or more of a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in copolymerization ratio More preferably, it is contained 5 mass% or more. The charge control resin has a glass transition temperature (Tg) of 35 ° C. to 90 ° C., a peak molecular weight (Mp) of 10,000 to 30,000, and a weight average molecular weight (Mn) of 25,000 to 50,000. is there. When this is used, preferable triboelectric charging characteristics can be imparted without affecting the thermal characteristics required for toner particles. Furthermore, since the charge control resin contains a sulfonic acid group, the dispersibility of the charge control resin itself in the dispersion of the colorant and the dispersibility of the colorant are improved, and the coloring power, transparency, and The triboelectric charging characteristics can be further improved.

  A polymerization initiator may be used to polymerize the polymerizable monomer. Examples of the polymerization initiator that can be used in the present invention include organic peroxide initiators and azo polymerization initiators.

  Examples of organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-) Butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butyl peroxy Oxy-2-ethylhexanoate, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, tert-butyl-peroxypivalate and the like can be mentioned.

  As an azo polymerization initiator, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile) And 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobismethylbutyronitrile, 2,2'-azobis- (methyl isobutyrate) and the like.

  Further, as a polymerization initiator, a redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides of persulfates (sodium salt, potassium salt and ammonium salt) and oxidizing metal salts of tetravalent cerium salt. Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (methylamine, and methylamine and ethylamine, etc.) Amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and reducible sulfur compounds of sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), Ascorbic acid or its salt, and lower aldehyde (C1-C6) are mentioned.

  The polymerization initiator is selected with reference to the 10 hour half-life temperature, and may be used alone or in combination. Although the addition amount of the said polymerization initiator changes with the polymerization degree made into the objective, generally 0.5 mass part or more and 20.0 mass parts or less are added with respect to 100 mass parts of polymerizable monomers.

  It is also possible to add further known chain transfer agents and polymerization inhibitors to control the degree of polymerization.

  When the polymerizable monomer is polymerized, various crosslinking agents can also be used. As a crosslinking agent, divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and trimethylol Polyfunctional compounds such as propane methacrylate are included.

  As a dispersion stabilizer used when preparing an aqueous medium, the dispersion stabilizer of a well-known inorganic compound and the dispersion stabilizer of an organic compound can be used. As a dispersion stabilizer for inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate And barium sulfate, bentonite, silica and alumina. On the other hand, dispersion stabilizers for organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and salts thereof, and starch. The use amount of these dispersion stabilizers is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  Among these dispersion stabilizers, when a dispersion stabilizer of an inorganic compound is used, a commercially available product may be used as it is, but in order to obtain a dispersion stabilizer having a finer particle size, the inorganic compound is preferably contained in an aqueous medium. It may be generated. For example, in the case of tricalcium phosphate, it can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high stirring.

  To the toner particles, an external additive may be externally added to impart various properties to the toner. Examples of the external additive for improving the flowability of the toner include fine inorganic powders such as fine silica powder, fine titanium oxide powder and fine powders of double oxides thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

The fine silica powder includes dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, a dry silica having a small amount of silanol groups on the surface and the inside of the fine silica powder and a small amount of Na ₂ O and SO ₃ ^2- is preferable. In addition, the dry silica may be a fine composite powder of silica and other metal oxides by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the production process.

  By subjecting the surface of the inorganic fine powder to a hydrophobization treatment with a treating agent, it is possible to achieve adjustment of the triboelectric charge of toner, improvement of environmental stability, and improvement of fluidity under high temperature and high humidity. Because of this, it is preferable to use a hydrophobicized inorganic fine powder. When the inorganic fine powder externally added to the toner absorbs moisture, the amount of triboelectric charge and fluidity of the toner are reduced, and the developability and the transferability are easily reduced.

  As a treating agent for hydrophobizing inorganic fine powder, unmodified silicone varnish, various modified silicone varnish, unmodified silicone oil, various modified silicone oil, silane compound, silane coupling agent, other organosilicon compounds, And organic titanium compounds. Among them, silicone oil is preferred. These treating agents may be used alone or in combination.

  The total amount of the inorganic fine powder added is preferably 1.0 to 5.0 parts by mass, and more preferably 1.0 to 2.5 parts by mass with respect to 100 parts by mass of toner particles. It is. The external additive preferably has a particle diameter of 1/10 or less of the average particle diameter of the toner particles from the viewpoint of toner durability.

  Hereinafter, methods of measuring various physical properties according to the present invention will be described.

<Method of measuring weight average particle diameter (D4), number average particle diameter (D1)>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated as follows. As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, a solution in which special grade sodium chloride is dissolved in ion exchange water so that the concentration is 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  In addition, before performing measurement and analysis, setting of dedicated software was performed as follows.

  In the "Change Standard Measurement Method (SOM)" screen of the special software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter, Make the obtained value. The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.

  In the dedicated software “pulse to particle size conversion setting” screen, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200 ml of the electrolytic aqueous solution in a 250 ml round bottom beaker for Multisizer 3 dedicated to a glass, set it on a sample stand, and stir the stirrer rod at 24 rotations / second counterclockwise. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.
(2) Into a 100 ml flat bottom beaker made of glass, 30 ml of the electrolytic aqueous solution is placed. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. 0.3 ml of a diluted solution obtained by diluting 3 times) with deionized water.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with 180 degrees of phase shift, and an ultrasonic dispersion device "Ultrasonic Dispensation System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and 2 ml of the contaminone N is added to the water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the aqueous electrolytic solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. Incidentally, in ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) In the round bottom beaker of (1) placed in the sample stand, the aqueous electrolyte solution of (5) in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to 5%. Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device to calculate the weight average particle diameter (D4) and the number average particle diameter (D1). The "average diameter" on the "Analytical / volume statistics (arithmetic mean)" screen is the weight average particle size (D4) when the graph / volume% is set in the special software, and the graph / number% in the special software The “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen when setting “1” is the number average particle diameter (D1).

<Measuring method of molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer are measured by gel permeation chromatography (GPC) as follows.

First, polyester A is dissolved in tetrahydrofuran (THF) at room temperature. Then, the resulting solution is filtered through a solvent-resistant membrane filter "Maechoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. It measures on condition of the following using this sample solution.
Device: High-speed GPC device "HLC-8220GPC" (manufactured by Tosoh Corp.)
Column: LF-604 double eluent: THF
Flow rate: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.020 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "(manufactured by Tosoh Co., Ltd.) are used to obtain molecular weight calibration curves.

<Method of measuring the number of polymerizable functional groups>
The number of polymerizable functional groups of the macromonomer was determined using the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) described above and the molecular weight (M_NMR) determined from nuclear magnetic resonance spectroscopy (1H-NMR) .

The measurement conditions of nuclear magnetic resonance spectroscopy (1H-NMR) [400 MHz, CDCl3, room temperature (25 ° C.)]
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by Nippon Denshi Co., Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Frequency range: 10500 Hz
Integration count: 64 times

  From the integral value of the obtained spectrum, the component ratio of the constituent monomer per one polymerizable functional group is determined. The NMR molecular weight (M_NMR) based on the polymerizable functional group can be calculated from the constituent ratio and the molecular weight of the monomer.

Furthermore, the number of polymerizable functional groups per molecule of macromonomer is calculated according to the following equation from the number average molecular weight (Mn) obtained from gel permeation chromatograph (GPC) and the NMR molecular weight (M_NMR) obtained from the above NMR. Can.
Polymerizable functional group number = GPC number average molecular weight (Mn) / NMR molecular weight (M_NMR)

<Measuring method of melting point>
The melting point (Tm) of the macromonomer is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat of fusion uses the heat of fusion of indium.

  Specifically, 3 mg of macromonomer is precisely weighed, put in an aluminum pan, and using a blank aluminum pan as a reference, the temperature rising rate is 10 within a measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is once raised to 200 ° C., then the temperature is lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature rising process is taken as the melting point (Tm) in the DSC measurement of the macromonomer of the present invention.

  Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited by the following examples. In the examples and comparative examples, parts and% are all based on mass unless otherwise noted.

<Production of Macromonomer 1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dehydrating pipe, and a pressure reducing device, 100.00 parts by mass of behenyl acrylate as a monomer, and VA-086 (Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. Eight parts were added and reacted at 60 ° C. for 5 hours under a nitrogen atmosphere to obtain a resin (1).

  Then, after the resin (1) obtained and 100.00 parts by mass of dehydrated chloroform were added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube and completely dissolved, triethylamine 2.00 A mass part was added and 2.80 mass parts of acryloyl chloride was gradually added, making it ice-cold. Then, it stirred at room temperature (25 degreeC) overnight.

  After reprecipitation with 300.0 parts by mass of methanol, filtration and drying were performed to obtain macromonomer 1. Physical properties of the obtained macromonomer 1 are shown in Table 2.

<Production of Macromonomer 2>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dehydrating pipe, and a pressure reducing device, 50.00 parts by mass of behenyl acrylate as a monomer, 42.5 parts by mass of stearyl acrylate, and VA-086 as an initiator 5.40 parts by mass of Wako Pure Chemical Industries, Ltd. was added, and reaction was performed at 100 ° C. for 5 hours under a nitrogen atmosphere to obtain a resin (2).

  Then, 100.00 parts by mass of tetrahydrofuran and 10 parts by mass of tetrahydrofuran were added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 40 ° C. to completely dissolve it. Thereafter, 2.40 parts by mass of 2-acryloyloxyethyl isocyanate was gradually added. Then, it stirred at 40 degreeC for 5 hours. Thereafter, THF was removed at 1 hPa, transferred from the reaction vessel to a vat, and after cooling, it was coarsely crushed to obtain macromonomer 2. Physical properties of the obtained macromonomer 2 are shown in Table 2.

<Production of Macromonomer 3>
A macromonomer 3 was obtained in the same manner as in the preparation of the macromonomer 2 except that the materials shown in Table 1 were changed. Physical properties of the obtained macromonomer 3 are shown in Table 2.

<Production of Macromonomers 4 and 6 to 18>
Macromonomers 4 and 6 to 18 were obtained in the same manner as the method for producing macromonomer 1 except that the starting materials shown in Table 1 were changed. The physical properties of the resulting macromonomers 4 and 6 to 18 are shown in Table 2.

<Production of Macromonomer 5>
In a jacketed stirring type continuous reaction tank for heat exchange, 100.00 parts by mass of behenyl acrylate and 0.1 parts by mass of di-t-butyl peroxide as a polymerization initiator are supplied at a constant speed, and the reaction temperature is stirred. Was maintained at a temperature of 250.degree. After 80% of the internal volume of the reaction vessel is filled with the reaction raw material, the outlet of the reaction vessel is opened to take out the reaction liquid according to the supply amount of the reaction raw material mixture, always 80% of the internal volume of the reaction vessel The reaction was continued while being filled with the reaction materials. The residence time of the reaction mixture in the reaction vessel was 15 minutes. The reaction mixture taken out of the reaction vessel is introduced into a thin film evaporator having a jacket heated to a temperature of 250 ° C. and a vacuum degree of 30 kPa, and contains volatile components including unreacted monomers and byproducts and macromonomer 5 Separated. Volatile components were recovered through a condenser, 80% of which was fed back to the reaction vessel with the reactant mixture. Physical properties of the macromonomer 5 thus obtained are shown in Table 2.

<Production of Toner 1>
9.0 parts by mass of tricalcium phosphate is added to 600.0 parts by mass of ion-exchanged water heated to a temperature of 60 ° C., and a TK homomixer (manufactured by Tokushu Kika Kogyo) is used at a stirring speed of 15,000 rpm Stir to prepare an aqueous medium.

Further, the following materials were mixed by a propeller type stirring device at a stirring speed of 100 rpm to prepare a solution.
Styrene 56.5 parts by mass n-Butyl acrylate 19.0 parts by mass Macromonomer 1 24.5 parts by mass

Next, in the above solution,
Cyan coloring agent (C.I. pigment blue 15: 3) 6.5 parts by mass Negatively charged control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.7 parts by mass Hydrocarbon wax (Tm = 78 ° C.) 9.0 parts by weight · Negative charge control resin 1 1.0 parts by weight (Styrene / 2-ethylhexyl acrylate / 2-acrylamido-2-methylpropane sulfonic acid copolymer, acid value 14.5 mg KOH / g, Tg = 83 ° C, Mw = 33,000)
-Polar resin 5.0 parts by mass (styrene / 2-hydroxyethyl methacrylate / methacrylic acid / methacrylic acid methyl copolymer, acid value 10 mg KOH / g, Tg = 80 ° C., Mw = 15,000)
Then, the mixture was heated to a temperature of 65 ° C., and then stirred with a TK homoxcer at a stirring speed of 10,000 rpm to dissolve and disperse, thereby preparing a polymerizable monomer composition. The amount of the polymerizable monomer composition was the total of styrene, n-butyl acrylate, macromonomer 1, cyan colorant, negative charge control agent, hydrocarbon wax, negative charge control resin 1, and polar resin 122 .2 parts by mass.

Subsequently, the polymerizable monomer composition is charged into the aqueous medium, and 6.0 parts by mass of perbutyl PV (10-hour half-life temperature 54.6 ° C. (made by NOF Corporation)) is added as a polymerization initiator. Using a TK homomixer at a temperature of 70 ° C., the mixture was stirred for 10 minutes at a stirring speed of 12,000 rpm for granulation.

  Transfer to a propeller-type stirrer and polymerize styrene, macromonomer 1 and n-butyl acrylate as polymerizable monomers in the polymerizable monomer composition at a temperature of 85 ° C. for 5 hours while stirring at a stirring speed of 200 rpm. The reaction was carried out to produce a slurry containing toner particles. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and stirring was performed for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with an amount of water 10 times that of the slurry, and after filtration and drying, the particle size was adjusted by classification to obtain toner particles.

Hydrophobic silica fine powder (primary particle diameter: 7 nm, BET specific surface area: 130 m) treated with 20% by mass of dimethylsilicone oil as external additive with respect to 100 parts by mass of the toner particles Toner 1 was obtained by mixing 1.5 parts by mass of H ² / g) with a Henschel mixer (manufactured by Mitsui Miike Kako Co., Ltd.) for 15 minutes at a stirring speed of 3000 rpm. Physical properties of Toner 1 are shown in Table 3.

<Production of Toners 2 to 24>
Toners 2 to 24 were obtained by the same manufacturing method as that of Toner 1 except for the changes as shown in Table 3. Physical properties of Toners 2 to 24 are shown in Table 3.

[Granulation property]
The value of weight average particle diameter (D4) and number average particle diameter (D1) ratio (D4 / D1) of “Coulter Counter Multisizer 3” was evaluated as an index of granulation. In the present invention, C or more is a level at which the effects of the present invention are obtained.

(Evaluation criteria)
A: D4 / D1 is less than 1.15 B: D4 / D1 is 1.15 or more and less than 1.25 C: D4 / D1 is 1.25 or more and less than 1.35 D: D4 / D1 is 1.35 or more

<Image evaluation>
The image evaluation was performed by partially modifying a commercially available color laser printer [HP Color LaserJet 3525 dn]. Modifications have been made to work with only one process cartridge installed. In addition, the fuser was remodeled so that it could be changed to any temperature.

  Remove the toner from the process cartridge for black toner installed in this color laser printer, clean the inside with air blow, introduce each toner (300 g) to the process cartridge, and refill the toner The process cartridge was mounted on a color laser printer, and the following image evaluation was performed. Specific image evaluation items are as follows.

Low temperature fixability
The image of a solid image (toning amount: 0.9 mg / cm ² ) was evaluated on a transfer material by changing the fixing temperature. The fixing temperature is a value obtained by measuring the surface of the fixing roller using a non-contact thermometer. As the transfer material, plain paper of LETTER size (XEROX 4200, manufactured by XEROX, 75 g / m ² ) was used.

(Evaluation criteria)
A: No offset at 100 ° C B: Offset at 100 ° C C: Offset at 110 ° C D: Offset at 120 ° C

[High temperature fixability]
An image of a solid image (toning amount: 0.9 mg / cm ² ) was evaluated on a transfer material at a fixing temperature (190 to 210 ° C.). The fixing temperature is a value obtained by measuring the surface of the fixing roller using a non-contact thermometer. As a transfer material, plain paper (Letter size XEROX 4200 paper, manufactured by XEROX, 75 g / m ² ) was used.

(Evaluation criteria)
A: No offset at 210 ° C B: Offset occurred at 210 ° C C: Offset generated at 200 ° C D: Offset generated at 190 ° C

〔Heat-resistant〕
5 g of each toner was placed in a 50 cc poly cup and left at a temperature of 55 ° C./humidity 10% RH for 3 days, and the presence or absence of aggregates was examined and evaluated.

(Evaluation criteria)
A: No clumps are generated B: Slight clumps are generated, Crushed when lightly pressed with a finger C: Clumps are generated, Crushed with a light finger D: Clumped completely

〔gross〕
The gloss value of the solid image (toning amount: 0.6 mg / cm ² ) was measured at a fixing temperature of 170 ° C. using PG-3D (manufactured by Nippon Denshoku Kogyo Co., Ltd.). As a transfer material, LETTER size plain paper (XEROX 4200 paper, manufactured by XEROX, 75 g / m ² ) was used.

(Evaluation criteria)
A: Gloss value 30 or more B: Gloss value 25 or more and less than 30 C: Gloss value 15 or more and less than 25 D: Gloss value less than 15

[Development streak]
Printout test of 25000 images of 1% printing ratio in horizontal line under normal temperature and normal humidity environment (temperature 23 ° C / humidity 60% RH) and high temperature and high humidity environment (temperature 33 ° C / humidity 85% RH) After completion, an image of halftone (toning amount: 0.6 mg / cm ² ) was printed out on LETTER size XEROX 4200 paper (manufactured by XEROX, 75 g / m ² ), and development streaks were evaluated.

(Evaluation criteria)
A: No occurrence B: 1 to 3 development streaks C: 4 to 6 development streaks D: 7 or more development streaks or 0.5 mm or more

[Examples 1 to 20]
In Examples 1 to 20, the above evaluation was performed using each of the toners 1 to 20 as the toner. The evaluation results are shown in Table 4.

Comparative Examples 1 to 4
In Comparative Examples 1 to 4, the above evaluation was performed using the toners 21 to 24 as the toner. The evaluation results are shown in Table 4.

Claims (2)

A method for producing a toner having toner particles containing a binder resin, comprising:
A step of dispersing a polymerizable monomer composition containing styrene and a macromonomer in an aqueous medium to form particles of the polymerizable monomer composition, and the particles of the polymerizable monomer composition Copolymerizing the styrene and the macromonomer to form the binder resin to obtain toner particles;
Have
The macromonomer is a macromonomer derived from alkyl acrylate or alkyl methacrylate,
The melting point (Tm) of the macromonomer in differential scanning calorimetry (DSC) measurement is 50 ° C. or more and 90 ° C. or less,
The method for producing a toner, wherein the polymerizable monomer composition contains the macromonomer in an amount of 3% by mass to 40% by mass. The toner manufacturing method of toner according to 請 Motomeko 1 that have a heat absorption peak or shoulder derived from the macromonomer in the measurement of DSC.